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Sommaire du brevet 2583007 

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Disponibilité de l'Abrégé et des Revendications

L'apparition de différences dans le texte et l'image des Revendications et de l'Abrégé dépend du moment auquel le document est publié. Les textes des Revendications et de l'Abrégé sont affichés :

  • lorsque la demande peut être examinée par le public;
  • lorsque le brevet est émis (délivrance).
(12) Brevet: (11) CA 2583007
(54) Titre français: AMINOPHOSPHINE
(54) Titre anglais: AMINO PHOSPHINE
Statut: Accordé et délivré
Données bibliographiques
(51) Classification internationale des brevets (CIB):
  • C07F 09/50 (2006.01)
(72) Inventeurs :
  • GAO, XIAOLIANG (Canada)
  • CARTER, CHARLES ASHTON GARRET (Canada)
  • FAN, LIANGYOU (Canada)
  • HENDERSON, LEE DOUGLAS (Canada)
(73) Titulaires :
  • NOVA CHEMICALS CORPORATION
(71) Demandeurs :
  • NOVA CHEMICALS CORPORATION (Canada)
(74) Agent: CLIFF BAARBAAR, CLIFF
(74) Co-agent:
(45) Délivré: 2015-03-31
(22) Date de dépôt: 2007-03-29
(41) Mise à la disponibilité du public: 2008-09-29
Requête d'examen: 2012-03-12
Licence disponible: S.O.
Cédé au domaine public: S.O.
(25) Langue des documents déposés: Anglais

Traité de coopération en matière de brevets (PCT): Non

(30) Données de priorité de la demande: S.O.

Abrégés

Abrégé français

Dans un mode de réalisation, cette invention fournit un ligand décrit par la formule : (ortho-F-C6H4)2PN(iPr)(ortho-F-C6H4)2. En combinaison avec i) une source de chrome et ii) un activateur tel que le méthalumoxane, le ligand de cette invention peut être utilisé pour préparer un produit doligomère qui contient un mélange dhexènes et doctènes. Les hexènes et octènes obtenus à laide de ce ligand contiennent de très faibles taux doléfines internes dans des conditions réactionnelles privilégiées.


Abrégé anglais


In one embodiment, this invention provides a ligand described by
the formula:
(ortho-F-C6H4)2PN(iPr)(ortho-F-C6H4)2
In combination with i) a source of chromium and ii) an activator such as
methalumoxane; the ligand of this invention may be used to prepare an
oligomer product that contains a mixture of hexenes and octenes. The
hexenes and octenes produced with this ligand contain very low levels of
internal olefins produced under preferred reaction conditions.

Revendications

Note : Les revendications sont présentées dans la langue officielle dans laquelle elles ont été soumises.


The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. The molecule:
<IMG>
wherein R is isopropyl.
2 A process for the oligomerization of ethylene to a mixture
comprising hexene-1 and octene-1, said process comprising contacting
ethylene under oligomerization reaction conditions with a catalyst system
to produce an oligomerization product comprising hexene-1 and octene-1,
said catalyst system comprising:
i) a source of chromium,
ii) a ligand defined by the formula
<IMG>

wherein each of R; and R1 to R16 is independently selected from the
group consisting of H and non-interfering substituents; wherein said
non-interfering substituents are selected from the group consisting
of hydrocarbyl substituents which contain from 1 to 30 carbon
atoms and heteroatom substituents which contain from 2 to 30
atoms;
and
iii) an activator.
3. The process of claim 2 wherein said activator is methalumoxane.
4. The process of claim 2 wherein said mixture comprising hexene-1
and octene-1 is further contacted with a polymerization catalyst.
5. The process of claim 2 wherein said mixture comprising hexene-1
and octene-1 is separated by distillation to produce a hexene-1 product.
6. The process of claim 5 wherein said distillation is undertaken in the
distillation system of a conventional alpha olefin plant and wherein said
mixture comprising hexene-1 and octene-1 is added to a crude alpha
olefin product from said conventional alpha olefin plant prior to being
added to said distillation system.
7. The process according to claim 2 wherein said mixture comprising
hexene-1 and octene-1 contains less than 10 weight% internal olefins.

8. The process according to claim 2 wherein said mixture comprising
hexene-1 and octene-1 contains at least 20 weight% octene-1.
9. The process according to claim 2 wherein said mixture comprising
hexene-1 and octene-1 contains less than 10 weight% internal olefins and
at least 20 weight% octene-1.
10. The process according to claim 2 when undertaken at a gauge
pressure of from 10 to 50 atmospheres.
11. The process according to claim 2 when undertaken at a
temperature of from 20 to 70°C.
12. The process according to claim 2 wherein each of said X1 to X4; ort1
to ort4 and R1 to R9 is hydrogen and R is isopropyl.
41

Description

Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.


CA 02583007 2007-03-29
FIELD OF THE INVENTION
This invention provides a new P-N-P ligand. The ligand is useful in
ethylene oligomerization reactions.
BACKGROUND OF THE INVENTION
Alpha olefins are commercially produced by the oligomerization of
ethylene in the presence of a simple alkyl aluminum catalyst (in the so
called "chain growth" process) or alternatively, in the presence of an
organometallic nickel catalyst (in the so called Shell Higher Olefins, or
"SHOP" process). Both of these processes typically produce a crude
oligomer product having a broad distribution of alpha olefins with an even
number of carbon atoms (i.e. butene-1, hexene-1, octene-1 etc.). The
various alpha olefins in the crude oligomer product are then typically
separated in a series of distillation columns. Butene-1 is generally the
least valuable of these olefins as it is also produced in large quantities as
a
by-product in various cracking and refining processes. Hexene-1 and
octene-1 often command comparatively high prices because these olefins
are in high demand as comonomers for linear low density polyethylene
(LLDPE).
Technology for the selective trimerization of ethylene to hexene-1
has been recently put into commercial use in response to the demand for
hexene-1. The patent literature discloses catalysts which comprise a
chromium source and a pyrrolide ligand as being useful for this process -
see, for example, United States Patent ("USP") 5,198,563 (Reagen et al.,
assigned to Phillips Petroleum).
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Another family of highly active trimerization catalysts is disclosed by
Wass et al. in WO 02/04119 (now United States Patents 7,143,633 and
6,800,702. The catalysts disclosed by Wass et al. are formed from a
chromium source and a chelating diphosphine ligand and are described in
further detail by Carter et al. (Chem. Comm. 2002, p 858-9). As described
in the Chem. Comm. paper, these catalysts preferably comprise a
diphosphine ligand in which both phosphine atoms are bonded to two
phenyl groups that are each substituted with an ortho-methoxy group.
Hexene-1 is produced with high activity and high selectivity by these
catalysts.
Similar diphosphine/tetraphenyl ligands are disclosed by Blann et
al. in W004/056478 and WO 04/056479 (now US 2006/0229480 and US
2006/0173226). However, in comparison to the ligands of Wass et al., the
disphosphine/tetraphenyl ligands disclosed by Blann et al. generally do not
contain polar substituents in ortho positions. The "tetraphenyl"
diphosphine ligands claimed in the '480 application must not have ortho
substituents (of any kind) on all four of the phenyl groups and the
"tetraphenyl" diphosphine ligands claimed in '226 are characterized by
having a polar substituent in a meta or para position. Both of these
approaches are shown to reduce the amount of hexenes produced and
increase the amount of octene (in comparison to the ligands of Wass et
al.). However, the hexene fraction generally contains a large portion of
internal hexenes, which is undesirable. Thus, chromium based catalysts
which contain the ligands of Wass et al. typically produce more octene
(which may be advantageous if demand for octene is high) but these
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CA 02583007 2007-03-29
ligands have the disadvantage of producing a hexene stream which is
contaminated with a comparatively large amount of internal olefins.
Internal olefins are undesirable contaminants in linear low density
polyethylene (LLDPE) production facilities because the internal olefins are
not readily incorporated into LLDPE with most transition metal catalysts.
Thus, it is preferable to remove/separate internal olefins from alpha olefins,
if the alpha olefin is to be used in an LLDPE process. As will be
appreciated by those skilled in the art, it is comparatively difficult to
separate hexene-1 from internal hexenes by distillation due to the close
boiling points of these hexene resins.
Accordingly, a process which selectively produces a mixture of
hexene-1 and octene-1 with very low levels of internal olefins represents a
desirable addition to the art.
SUMMARY OF THE INVENTION
In one embodiment, the present invention provides a new molecule
defined by the formula:
R
F I F*,--
\
~
P \--P
F F
wherein R is isopropyl.
The molecule is particularly suitable for use as a ligand in a process
to oligomerize ethylene. Potential alternative uses include ligands for
hydrogenation and/or hydroformylation reactions.
Attempts to produce the new molecule by conventional
condensation reactions (i.e., using a precursor amine and a precursor
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CA 02583007 2007-03-29
diphosphine chloride) were unsuccessful. Accordingly, another
embodiment of this invention provides a new synthetic route to this
molecule. A preferred synthesis uses a molecule defined by the formula
(ortho - F - C6H4)2PX wherein X is chlorine and bromine and is described
in more detail in the Examples.
Another embodiment of this invention provides a process to
oligomerize ethylene. A process for the selective oligomerization of
ethylene to a mixture comprising hexene-1 and octene-1, said process
comprising contacting ethylene under oligomerization reaction conditions
with a catalyst system to produce an oligomerization product comprising
hexene-1 and octene-1, said catalyst system comprising:
i) a source of chromium;
ii) a ligand defined by the formula
R3 R6
R2 R X2 R5
X1
R~ Ra
O rt, P/ P O rtz
Xq X3
O rtq O rtg
R12 R7
Rlo R9 R
R~~ a
wherein each of X, to X4 is independently selected from the group
consisting of F, Br, or Cl; and each of R; ort' to ort4 and R, to R12 is
independently selected from the group consisting of H and "non-
interfering substituents" (i.e. substituents that do not interfere with
the oligomerization reaction);
and
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CA 02583007 2007-03-29
iii) an activator.
In general, the ligand used in the oligomerization process of this
invention has four ortho halide substituents - more specifically, each of the
four phenyl groups has an ortho halide substituent. In the most general
sense, each of ort' to ort4, X, to X4 and R, to R12 are hydrogen or "non-
interfering substituents" (wherein the term simply means that the
substituents do not interfere with the oligomerization process).
The oligomerization process of this invention may be conducted
under conventional oligomerization conditions. One important advantage
of the present invention is that the product olefins can comprise a
desirable mixture of hexene and octene (in particular, greater than 80
weight% of the ethylene that is converted to a liquid product during the
process can be hexenes and octenes) with very low levels of internal
olefins (preferably less than 15 weight% of the mixed hexene and octene
stream is internal olefins) when the process is conducted under preferred
temperature and pressure conditions.
DETAILED DESCRIPTION OF THE PREFERRED
EMBODIMENTS
PART A CATALYST SYSTEM
The catalyst system used in the process of the present invention
must contain three essential components, namely:
(i) a source of chromium:
(ii) amino diphosphine ligand; and
(iii) an activator.
Preferred forms of each of these components are discussed below.
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CA 02583007 2007-03-29
Chromium Source ("Component (i)")
Any source of chromium which allows the oligomerization process
of the present invention to proceed may be used. Preferred chromium
sources include chromium trichloride; chromium (III) 2-ethylhexanoate;
chromium (III) acetylacetonate and chromium carboxyl complexes such as
chromium hexacarboxyl.
Ligand Used in the Oligomerization Process ("Component (ii)")
In general, the ligand used in the oligomerization process of this
invention is defined by the formula:
R3 R6
R2 X1 R X2 AR,5
R1 I Ra
Ort1 P/ P Ort2
Xq x3
Ort4 Ort3
R12 R7
R10 R9 R
R11 8
wherein each of X1 to X4 is independently selected from the group
consisting of F, Br, or Cl; and each of R; ort1 to ort4 and R1 to R12 is
independently selected from the group consisting of H and "non-interfering
substituents" (i.e. substituents that do not interfere with the
oligomerization
reaction).
Each of X1 to X4 is preferably fluorine.
R is preferably a hydrocarbyl group having from 1 to 30 carbon
atoms. The hydrocarbyl groups may contain heteroatom substituents
(having a heteroatom selected from 0, N, P and S). Simple alkyl groups
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CA 02583007 2007-03-29
having from 1 to 12 carbon atoms are preferred. Isopropyl is particularly
preferred.
Each of ort' to ort4 is preferably selected from the group consisting
of H, Br, Cl, F and small alkyl groups (having from 1 to 3 carbon atoms). H
is most preferred.
Each of R, to R12 is independently selected from the group
consisting of H, hydrocarbyl substituents which contain from 1 to 30
carbon atoms (which hydrocarbyl substituents may contain heteroatoms
selected from the group consisting of 0, N, P and S) and heteroatom
substituents (i.e. substituents which are bonded to the phenyl ring via an
0, N, P or S atom) which contain from 2 to 30 atoms. It is preferred that
R, to R12 are not polar substituents. It is especially preferred that each of
R, to R12 is selected from H and C, to C6 alkyls or C6 to C12 aryls.
Activator ("Component (iii)")
The activator (component (iii)) may be any compound that
generates an active catalyst for ethylene oligomerization with components
(i) and (ii). Mixtures of activators may also be used. Suitable compounds
include organoaluminum compounds, organoboron compounds and
inorganic acids and salts, such as tetrafluoroboric acid etherate, silver
tetrafluoroborate, sodium hexafluoroantimonate and the like. Suitable
organoaluminium compounds include compounds of the formula AIR3,
where each R is independently C, -C12 alkyl, oxygen or halide, and
compounds such as LiAIH4 and the like. Examples include
trimethylaluminium (TMA), triethylaluminium (TEA), tri-isobutylaluminium
(TIBA), tri-n-octylaluminium, methylaluminium dichloride, ethylaluminium
8
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CA 02583007 2007-03-29
dichloride, dimethylaluminium chloride, diethylaluminium chloride,
ethylaluminiumsesquichloride, methylaluminiumsesquichloride, and
alumoxanes. Alumoxanes are well known in the art as typically oligomeric
compounds which can be prepared by the controlled addition of water to
an alkylaluminium compound, for example trimethylaluminium. Such
compounds can be linear, cyclic, cages or mixtures thereof. Commercially
available alumoxanes are generally believed to be mixtures of linear and
cyclic compounds. The cyclic alumoxanes can be represented by the
formula [R6AIO]S and the linear alumoxanes by the formula R7(R8AIO)S
wherein s is a number from about 2 to 50, and wherein R6, R7, and R$
represent hydrocarbyl groups, preferably C, to C6 alkyl groups, for
example methyl, ethyl or butyl groups. Alkylalumoxanes especially
methylalumoxane (MAO) are preferred.
It will be recognized by those skilled in the art that commercially
available alkylalumoxanes may contain a proportion of trialkylaluminium.
For instance, commercial MAO usually contains approximately 10 wt %
trimethylaluminium (TMA), and commercial "modified MAO" (or "MMAO")
contains both TMA and TIBA. Quantities of alkylalumoxane are generally
quoted herein on a molar basis of aluminium (and include such "free"
trialkylaluminium).
Examples of suitable organoboron compounds are boroxines,
NaBH4, trimethylboron, triethylboron,
dimethylphenylammoniumtetra(phenyl)borate, trityltetra(phenyl)borate,
triphenylboron, dimethylphenylammonium tetra(pentafluorophenyl)borate,
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sodium tetrakis[(bis-3,5-trifluoromethyl)phenyl]borate,
trityltetra(pentafluorophenyl)borate and tris(pentafluorophenyl) boron.
Activator compound (iii) may also be or contain a compound that
acts as a reducing or oxidizing agent, such as sodium or zinc metal and
the like, or oxygen and the like.
In the preparation of the catalyst systems used in the present
invention, the quantity of activating compound to be employed is easily
determined by simple testing, for example, by the preparation of small test
samples which can be used to oligimerize small quantities of ethylene and
thus to determine the activity of the produced catalyst. It is generally
found that the quantity employed is sufficient to provide 0.5 to 1000 moles
of aluminium (or boron) per mole of chromium. MAO is the presently
preferred activator. Molar Al/Cr ratios of from 1/1 to 500/1 are preferred.
PART B PROCESS CONDITIONS
The chromium (component (i)) and ligand (component (ii)) may be
present in any molar ratio which produces oligomer, preferably between
100:1 and 1:100, and most preferably from 10:1 to 1:10, particularly 3:1 to
1:3. Generally the amounts of (i) and (ii) are approximately equal, i.e. a
ratio of between 1.5:1 and 1:1.5.
Components (i)-(iii) of the catalyst system utilized in the present
invention may be added together simultaneously or sequentially, in any
order, and in the presence or absence of ethylene in any suitable solvent,
so as to give an active catalyst. For example, components (i), (ii) and (iii)
and ethylene may be contacted together simultaneously, or components
(i), (ii) and (iii) may be added together simultaneously or sequentially in
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CA 02583007 2007-03-29
any order and then contacted with ethylene, or components (i) and (ii) may
be added together to form an isolable metal-ligand complex and then
added to component (iii) and contacted with ethylene, or components (i),
(ii) and (iii) may be added together to form an isolable metal-ligand
complex and then contacted with ethylene. Suitable solvents for
contacting the components of the catalyst or catalyst system include, but
are not limited to, hydrocarbon solvents such as heptane, toluene, 1-
hexene and the like, and polar solvents such as diethyl ether,
tetrahydrofuran, acetonitrile, dichloromethane, chloroform, chlorobenzene,
methanol, acetone and the like.
The catalyst components (i), (ii) and (iii) utilized in the present
invention can be unsupported or supported on a support material, for
example, silica, alumina, MgC12 or zirconia, or on a polymer, for example
polyethylene, polypropylene, polystyrene, or poly(aminostyrene). If
desired the catalysts can be formed in situ in the presence of the support
material, or the support material can be pre-impregnated or premixed,
simultaneously or sequentially, with one or more of the catalyst
components. The quantity of support material employed can vary widely,
for example from 100,000 to 1 grams per gram of metal present in the
transition metal compound. In some cases, the support may material can
also act as or as a component of the activator compound (iii). Examples
include supports containing alumoxane moieties.
The oligomerization can be, conducted under solution phase, slurry
phase, gas phase or bulk phase conditions. Suitable temperatures range
from 100 C to +300 C preferably from 100 C to 1000 C, especially from 20
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CA 02583007 2007-03-29
to 70 C. Suitable pressures are from atmospheric to 800 atmospheres
(gauge) preferably from 5 atmospheres to 100 atmospheres, especially
from 10 to 50 atmospheres.
Irrespective of the process conditions employed, the oligomerization
is typically carried out under conditions that substantially exclude oxygen,
water, and other materials that act as catalyst poisons. Also,
oligomerization can be carried out in the presence of additives to control
selectivity, enhance activity and reduce the amount of polymer formed in
oligomerization processes. Potentially suitable additives include, but are
not limited to, hydrogen or a halide source.
There exist a number of options for the oligomerization reactor
including batch, semi-batch, and continuous operation. The reactions of
the present invention can be performed under a range of process
conditions that are readily apparent to those skilled in the art: as a
homogeneous liquid phase reaction in the presence or absence of an inert
hydrocarbon diluent such as toluene or heptanes; as a two-phase
liquid/liquid reaction; as a slurry process where the catalyst is in a form
that displays little or no solubility; as a bulk process in which essentially
neat reactant and/or product olefins serve as the dominant medium; as a
gas-phase process in which at least a portion of the reactant or product
olefin(s) are transported to or from a supported form of the catalyst via the
gaseous state. Evaporative cooling from one or more monomers or inert
volatile liquids is but one method that can be employed to effect the
removal of heat from the reaction. The reactions may be performed in the
known types of gas-phase reactors, such as circulating bed, vertically or
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horizontally stirred-bed, fixed-bed, or fluidized-bed reactors, liquid-phase
reactors, such as plug-flow, continuously stirred tank, or loop reactors, or
combinations thereof. A wide range of methods for effecting product,
reactant, and catalyst separation and/or purification are known to those
skilled in the art and may be employed: distillation, filtration, liquid-
liquid
separation, slurry settling, extraction, etc. One or more of these methods
may be performed separately from the oligomerization reaction or it may
be advantageous to integrate at least some with the reaction; a non-
limiting example of this would be a process employing catalytic (or
reactive) distillation. Also advantageous may be a process which includes
more than one reactor, a catalyst kill system between reactors or after the
final reactor, or an integrated reactor/separator/purifier. While all catalyst
components, reactants, inerts, and products could be employed in the
present invention on a once-through basis, it is often economically
advantageous to recycle one or more of these materials; in the case of the
catalyst system, this might require reconstituting one or more of the
catalysts components to achieve the active catalyst system. It is within the
scope of this invention that an oligomerization product might also serve as
a solvent or diluent. Mixtures of inert diluents or solvents also could be
employed. The preferred diluents or solvents are aliphatic and aromatic
hydrocarbons and halogenated hydrocarbons such as, for example,
isobutane, pentane, toluene, xylene, ethylbenzene, cumene, mesitylene,
heptane, cyclohexane, methylcyclohexane, 1-hexene, 1-octene,
chlorobenzene, dichlorobenzene, and the like, and mixtures such as
IsoparTM
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Techniques for varying the distribution of products from the
oligomerization reactions include controlling process conditions (e.g.
concentration of components (i)-(iii), reaction temperature, pressure,
residence time) and properly selecting the design of the process and are
well known to those skilled in the art.
The ethylene feedstock for the oligomerization may be substantially
pure or may contain other olefinic impurities and/or ethane. One
embodiment of the process of the invention comprises the oligomerization
of ethylene-containing waste streams from other chemical processes or a
crude ethylene/ethane mixture from a cracker.
In a highly preferred embodiment of the present invention, the
oligomerization product produced from this invention is added to a product
stream from another alpha olefins manufacturing process for separation
into different alpha olefins. As previously discussed, "conventional alpha
olefin plants" (wherein the term includes i) those processes which produce
alpha olefins by a chain growth process using an aluminum alkyl catalyst,
ii) the aforementioned "SHOP" process and iii) the production of olefins
from synthesis gas using the so called Lurgi process) have a series of
distillation columns to separate the "crude alpha product" (i.e. a mixture of
alpha olefins) into alpha olefins (such as butene-1, hexene-1 and octene-
1). The mixed hexene-octene product which is produced in accordance
with the present invention is highly suitable for addition/mixing with a crude
alpha olefin product from an existing alpha olefin plant (or a "cut" or
fraction of the product from such a plant) because the mixed hexene-
octene product produced in accordance with the present invention can
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have very low levels of internal olefins. Thus, the hexene-octene product
of the present invention can be readily separated in the existing distillation
columns of alpha olefin plants (without causing the large burden on the
operation of these distillation columns which would otherwise exist if the
present hexene-octene product stream contained large quantities of
internal olefins). As used herein, the term "liquid product" is meant to refer
to the oligomers produced by the process of the present invention which
have from 4 to (about) 20 carbon atoms.
The liquid product from the oligomerization process of the present
invention preferably consists of from 20 to 80 weight% octenes (especially
from 35 to 75 weight%) octenes and from 15 to 50 weight% (especially
from 20 to 40 weight%) hexenes (where all of the weight% are calculated
on the basis of the liquid product by 100%.
The preferred oligomerization process of this invention is also
characterized by producing very low levels of internal olefins (i.e. low
levels of hexene-2, hexene-3, octene-2, octene-3 etc.), with preferred
levels of less than 10 weight% (especially less than 5 weight%) of the
hexenes and octenes being internal olefins.
One embodiment of the present invention encompasses the use of
components (i) (ii) and (iii) in conjunction with one or more types of olefin
polymerization catalyst system (iv) to trimerise ethylene and subsequently
incorporate a portion of the trimerisation product(s) into a higher polymer.
Component (iv) may be one or more suitable polymerization
catalyst system(s), examples of which include, but are not limited to,
conventional Ziegler-Natta catalysts, metallocene catalysts,
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monocyclopentadienyl or "constrained geometry" catalysts, phosphinimine
catalysts, heat activated supported chromium oxide catalysts (e.g.
"Phillips"-type catalysts), late transition metal polymerization catalysts
(eg.
diimine, diphosphine and salicylaidimine nickel/palladium catalysts, iron
and cobalt pyridyldiimine catalysts and the like) and other so-called "single
site catalysts" (SSC's).
Ziegler-Natta catalysts, in general, consist of two main components.
One component is an alkyl or hydride of a Group I to III metal, most
commonly AI(Et)3 or AI(iBu)3 or AI(Et)2CI but also encompassing Grignard
reagents, n-butyllithium, or dialkylzinc compounds. The second
component is a salt of a Group IV to VIII transition metal, most commonly
halides of titanium or vanadium such as TiC14, TiCl3, VC14, or VOCI3. The
catalyst components when mixed, usually in a hydrocarbon solvent, may
form a homogeneous or heterogeneous product. Such catalysts may be
impregnated on a support, if desired, by means known to those skilled in
the art and so used in any of the major processes known for co-ordination
catalysis of polyolefins such as solution, slurry, and gas-phase. In addition
to the two major components described above, amounts of other
compounds (typically electron donors) maybe added to further modify the
polymerization behaviour or activity of the catalyst.
Metallocene catalysts, in general, consist of transition metal
complexes, most commonly based on Group IV metals, ligated with
cyclopentadienyl(Cp)-type groups. A wide range of structures of this type
of catalysts is known, including those with substituted, linked and/or
heteroatom-containing Cp groups, Cp groups fused to other ring systems
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and the like. Additional activators, such as boranes or alumoxane, are
often used and the catalysts may be supported, if desired.
Monocyclopentadienyl or "constrained geometry" catalysts, in
general, consist of a transition metal complexes, most commonly based on
Group IV metals, ligated with one cyclopentadienyl(Cp)-type group, often
linked to additional donor group. A wide range of structures of this type of'
catalyst is known, including those with substituted, linked and/or
heteroatom-containing Cp groups, Cp groups fused to other ring systems
and a range of linked and non-linked additional donor groups such as
amides, amines and alkoxides. Additional activators, such as boranes or
alumoxane, are often used and the catalysts may be supported, if desired.
A typical heat activated chromium oxide (Phillips) type catalyst
employs a combination of a support material to which has first been added
a chromium-containing material wherein at least part of the chromium is ini
the hexavalent state by heating in the presence of molecular oxygen. The
support is generally composed of about 80 to 100 wt. % silica, the
remainder, if any, being selected from the group consisting of refractory
metal oxides, such as aluminium, boria, magnesia, thoria, zirconia, titania
and mixtures of two or more of these refractory metal oxides. Supports
can also comprise alumina, aluminium phosphate, boron phosphate and
mixtures thereof with each other or with silica. The chromium compound
is typically added to the support as a chromium (III) compound such as the
acetate or acetylacetonate in order to avoid the toxicity of chromium (VI).
The raw catalyst is then calcined in air at a temperature between 250 and
1000 C. for a period of from a few seconds to several hours. This
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converts at least part of the chromium to the hexavalent state. Reduction
of the Cr (VI) to its active form normally occurs in the polymerization
reaction, but can be done at the end of the calcination cycle with CO at
about 350 C. Additional compounds, such as fluorine, aluminium and/or
titanium may be added to the raw Phillips catalyst to modify it.
Late transition metal and single site catalysts cover a wide range of
catalyst structures based on metals across the transition series.
Component (iv) may also comprise one or more polymerization
catalysts or catalyst systems together with one or more additional
oligomerization catalysts or catalyst systems. Suitable oligomerization
catalysts include, but are not limited to, those that dimerise (for example,
nickel phosphine dimerisation catalysts) or trimerise olefins or otherwise
oligomerize olefins to, for example, a broader distribution of 1-olefins (for
example, iron and cobalt pyridyldiimine oligomerization catalysts).
Component (iv) may independently be supported or unsupported.
Where components (i) and (ii) and optionally (iii) are supported, (iv) may
be co-supported sequentially in any order or simultaneously on the same
support or may be on a separate support. For some combinations, the
components (i) (iii) may be part or all of component (iv). For example, if
component (iv) is a heat activated chromium oxide catalyst then this may
be (i), a chromium source and if component (iv) contains an alumoxane
activator then this may also be the optional activator (iii).
The components (i), (ii), (iii) and (iv) may be in essentially any molar
ratio that produces a polymer product. The precise ratio required depends
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on the relative reactivity of the components and also on the desired
properties of the product or catalyst systems.
An "in series" process could be conducted by first conducting the
oligomerization reaction, then passing the oligomerization product to a
polymerization reaction. In the case of an "in series" process various
purification, analysis and control steps for the oligomeric product could
potentially be incorporated between the trimerization and subsequent
reaction stages. Recycling between reactors configured in series is also
possible. An example of such a process would be the oligomerization of
ethylene in a single reactor with a catalyst comprising components (i)-(iii)
followed by co-polymerization of the oligomerization product with ethylene
in a separate, linked reactor to give branched polyethylene. Another
example would be the oligomerization of an ethylene-containing waste
stream from a polyethylene process, followed by introduction of the
oligomerization product back into the polyethylene process as a co-
monomer for the production of branched polyethylene.
An example of an "in situ" process is the production of branched
polyethylene catalyzed by components (i)-(iv), added in any order such
that the active catalytic species derived from components (i)-(iii) are at
some point present in a reactor with component (iv).
Both the "in series and "in situ" approaches can be adaptions of
current polymerization technology for the process stages including
component (iv). All major olefin existing polymerization processes,
including multiple reactor processes, are considered adaptable to this
approach. One adaption is the incorporation of an oligomerization catalyst
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bed into a recycle loop of a gas phase polymerization process, this could
be as a side or recycle stream within the main fluidization recycle loop anci
or within the degassing recovery and recycle system.
Polymerization conditions when component (iv) is present can be,
for example, solution phase, slurry phase, gas phase or bulk phase, with
temperatures ranging from -100 C. to +300 C., and at pressures of
atmospheric and above, particularly from 1.5 to 50 atmospheres. Reaction
conditions, will typically have a significant impact upon the properties (e.g.
density, melt index, yield) of the polymer being made and it is likely that
the polymer requirements will dictate many of the reaction variables.
Reaction temperature, particularly in processes where it is important to
operate below the sintering temperature of the polymer, will typically, and
preferably, be primarily selected to optimize the polymerization reaction
conditions. Also, polymerization or copolymerization can be carried out in
the presence of additives to control polymer or copolymer molecular
weights. The use of hydrogen gas as a means of controlling the average
molecular weight of the polymer or copolymer applies generally to the
polymerization process of the present invention.
Slurry phase polymerization conditions or gas phase polymerization
conditions are particularly useful for the production of high or low density
grades of polyethylene, and polypropylene. In these processes the
polymerization conditions can be batch, continuous or semi-continuous.
Furthermore, one or more reactors may be used, e.g. from two to five
reactors in series. Different reaction conditions, such as different
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temperatures or hydrogen concentrations may be employed in the differerit
reactors.
Once the polymer product is discharged from the reactor, any
associated and absorbed hydrocarbons are substantially removed, or
degassed, from the polymer by, for example, pressure let-down or gas
purging using fresh or recycled steam, nitrogen or light hydrocarbons
(such as ethylene). Recovered gaseous or liquid hydrocarbons may be
recycled to a purification system or the polymerization zone.
In the slurry phase polymerization process the polymerization
diluent is compatible with the polymer(s) and catalysts, and may be an
alkane such as hexane, heptane, isobutane, or a mixture of hydrocarbons
or paraffins. The polymerization zone can be, for example, an autoclave
or similar reaction vessel, or a continuous liquid full loop reactor, e.g. of
the type well-known in the manufacture of polyethylene by the Phillips
Process. When the polymerization process of the present invention is
carried out under slurry conditions the polymerization is preferably carried
out at a temperature above 0° C., most preferably above 15 C.
Under slurry conditions the polymerization temperature is preferably
maintained below the temperature at which the polymer commences to
soften or sinter in the presence of the polymerization diluent. If the
temperature is allowed to go above the latter temperature, fouling of the
reactor can occur. Adjustment of the polymerization within these defined
temperature ranges can provide a useful means of controlling the average
molecular weight of the produced polymer. A further useful means of
controlling the molecular weight is to conduct the polymerization in the
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presence of hydrogen gas which acts as chain transfer agent. Generally,
the higher the concentration of hydrogen employed, the lower the average
molecular weight of the produced polymer.
In bulk polymerization processes, liquid monomer such as
propylene is used as the polymerization medium.
Methods for operating gas phase polymerization processes are we91
known in the art. Such methods generally involve agitating (e.g. by
stirring, vibrating or fluidizing) a bed of catalyst, or a bed of the target
polymer (i.e. polymer having the same or similar physical properties to that
which it is desired to make in the polymerization process) containing a
catalyst, and feeding thereto a stream of monomer (under conditions such
that at least part of the monomer polymerizes in contact with the catalyst in
the bed. The bed is generally cooled by the addition of cool gas (e.g.
recycled gaseous monomer) and/or volatile liquid (e.g. a volatile inert
hydrocarbon, or gaseous monomer which has been condensed to form a
liquid). The polymer produced in, and isolated from, gas phase processes
forms directly a solid in the polymerization zone and is free from, or
substantially free from liquid. As is well known to those skilled in the art,
if
any liquid is allowed to enter the polymerization zone of a gas phase
polymerization process the quantity of liquid in the polymerization zone is
small in relation to the quantity of polymer present. This is in contrast to
"solution phase" processes wherein the polymer is formed dissolved in a
solvent, and "slurry phase" processes wherein the polymer forms as a
suspension in a liquid diluent.
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The gas phase process can be operated under batch, semi-batch,
or so-called "continuous" conditions. It is preferred to operate under
conditions such that monomer is continuously recycled to an agitated
polymerization zone containing polymerization catalyst, make-up monomer
being provided to replace polymerized monomer, and continuously or
intermittently withdrawing produced polymer from the polymerization zone
at a rate comparable to the rate of formation of the polymer, fresh catalyst
being added to the polymerization zone to replace the catalyst withdrawn
from the polymerization zone with the produced polymer.
Methods for operating gas phase fluidized bed processes for
making polyethylene, ethylene copolymers and polypropylene are well
known in the art. The process can be operated, for example, in a vertical
cylindrical reactor equipped with a perforated distribution plate to support
the bed and to distribute the incoming fluidizing gas stream through the
bed. The fluidizing gas circulating through the bed serves to remove the
heat of polymerization from the bed and to supply monomer for
polymerization in the bed. Thus the fluidizing gas generally comprises the
monomer(s) normally together with some inert gas (e.g. nitrogen or inert
hydrocarbons such as methane, ethane, propane, butane, pentane or
hexane) and optionally with hydrogen as molecular weight modifier. The
hot fluidizing gas emerging from the top of the bed is led optionally through
a velocity reduction zone (this can be a cylindrical portion of the reactor
having a wider diameter) and, if desired, a cyclone and or filters to
disentrain fine solid particles from the gas stream. The hot gas is then Ied
to a heat exchanger to remove at least part of the heat of polymerization.
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Catalysts are preferably fed continuously or at regular internals to the bed.
At start up of the process, the bed comprises fluidizable polymer which is
preferably similar to the target polymer. Polymer is produced continuously
within the bed by the polymerization of the monomer(s). Preferably means
are provided to discharge polymer from the bed continuously or at regular
internals to maintain the fluidized bed at the desired height. The process
is generally operated at relatively low pressure, for example, at 10 to 50
atmospheres, and at temperatures for example, between 50 and 1350 C.
The temperature of the bed is maintained below the sintering temperature
of the fluidized polymer to avoid problems of aggiomeration.
In the gas phase fluidized bed process for polymerization of olefins
the heat evolved by the exothermic polymerization reaction is normally
removed from the polymerization zone (i.e. the fluidized bed) by means of
the fluidizing gas stream as described above. The hot reactor gas
emerging from the top of the bed is led through one or more heat
exchangers wherein the gas is cooled. The cooled reactor gas, together
with any make-up gas, is then recycled to the base of the bed. In the gas
phase fluidized bed polymerization process of the present invention it is
desirable to provide additional cooling of the bed (and thereby improve the
space time yield of the process) by feeding a volatile liquid to the bed
under conditions such that the liquid evaporates in the bed thereby
absorbing additional heat of polymerization from the bed by the "latent
heat of evaporation" effect. When the hot recycle gas from the bed enters
the beat exchanger, the volatile liquid can condense out. In one
embodiment of the present invention the volatile liquid is separated from
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the recycle gas and reintroduced separately into the bed. Thus, for
example, the volatile liquid can be separated and sprayed into the bed. In
another embodiment of the present invention the volatile liquid is recycled
to the bed with the recycle gas. Thus the volatile liquid can be condensed
from the fluidizing gas stream emerging from the reactor and can be
recycled to the bed with recycle gas, or can be separated from the recycle
gas and then returned to the bed.
A number of process options can be envisaged when using the
catalysts of the present invention in an integrated process to prepare
higher polymers i.e. when component (iv) is present. These options
include "in series" processes in which the oligomerization and subsequent
polymerization are carried in separate but linked reactors and "in situ"
processes in which a both reaction steps are carried out in the same
reactor.
In the case of a gas phase "in situ" polymerization process,
component (iv) can, for example, be introduced into the polymerization
reaction zone in liquid form, for example, as a solution in a substantially
inert liquid diluent. Components (i)-(iv) may be independently added to any
part of the polymerization reactor simultaneously or sequentially together
or separately. Under these circumstances it is preferred the liquid
containing the component(s) is sprayed as fine droplets into the
polymerization zone. The droplet diameter is preferably within the range 1
to 1000 microns.
Although not usually required, upon completion of polymerization or
copolymerization, or when it is desired to terminate polymerization or
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copolymerization or at least temporarily deactivate the catalyst or catalyst
component of this invention, the catalyst can be contacted with water,
alcohols, acetone, or other suitable catalyst deactivators a manner known
to persons of skill in the art.
A range of polyethylene polymers are considered accessible
including high density polyethylene, medium density polyethylene, low
density polyethylene, ultra low density polyethylene and elastomeric
materials. Particularly important are the polymers having a density in the
range of 0.91 to 0.93, grams per cubic centimeter (g/cc) generally referred
to in the art as linear low density polyethylene. Such polymers and
copolymers are used extensively in the manufacture of flexible blown or
cast film.
Depending upon the use of the polymer product, minor amounts of
additives are typically incorporated into the polymer formulation such as
acid scavengers, antioxidants, stabilizers, and the like. Generally, these
additives are incorporated at levels of about 25 to 2000 parts per million by
weight (ppm), typically from about 50 to about 1000 ppm, and more
typically 400 to 1000 ppm, based on the polymer. In use, polymers or
copolymers made according to the invention in the form of a powder are
conventionally compounded into pellets. Examples of uses for polymer
compositions made according to the invention include use to form fibres,
extruded films, tapes, spunbonded webs, molded or thermoformed
products, and the like. The polymers may be blown or cast into films, or
may be used for making a variety of molded or extruded articles such as
pipes, and containers such as bottles or drums. Specific additive
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packages for each application may be selected as known in the art.
Examples of supplemental additives include slip agents, anti-blocks, anti-
stats, mould release agents, primary and secondary anti-oxidants,
clarifiers, nucleants, uv stabilizers, and the like. Classes of additives are
well known in the art and include phosphite antioxidants, hydroxylamine
(such as N,N-dialkyl hydroxylamine) and amine oxide (such as dialkyl
methyl amine oxide) antioxidants, hindered amine light (uv) stabilizers,
phenolic stabilizers, benzofuranone stabilizers, and the like.
Fillers such as silica, glass fibers, talc, and the like, nucleating
agents, and colourants also may be added to the polymer compositions as
known by the art.
The present invention is illustrated in more detail by the following
non-limiting examples.
EXAMPLES
The following abbreviations are used in the examples:
A = Angstrom units
NMR = nuclear magnetic resonance
Et = ethyl
Bu = butyl
iPr = isopropyl
c= comparative
rpm = revolutions per minute
GC = gas chromatography
RX = reaction
Wt = weight
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Ca's = butenes
C6's = hexenes
C$'s = octenes
PE = polyethylene
Ligand Synthesis
General
All reactions involving air and or moisture sensitive compounds
were conducted under nitrogen using standard Schlenk or cannula
techniques, or in a glovebox. Reaction solvents were purified prior to use
(e.g. by distillation) and stored over activated 4 A sieves. Diethylamine,
triethylamine and isopropylamine were purchased from Aldrich and dried
over 4 A molecular sieves prior to use. 1-Bromo-2-fluoro-benzene,
phosphorus trichloride (PCI3), hydrogen chloride gas and n-butyllithium
were purchased from Aldrich and used as is. The methalumoxane (MAO),
10 wt% Al in toluene, was purchased from Akzo and used as is.
Deuterated solvents were purchased (toluene-d8, THF-d8) and were stored
over 4 A sieves. NMR spectra were recorded on a Bruker 300 MHz
spectrometer (300.1 MHz for'H, 121.5 MHz for 31P, 282.4 for19F).
Preparation of Et2NPCI2
Et2NH (50.00 mmol, 5.17 mL) was added dropwise to a solution of
PCI3 (25.00 mmol, 2.18 mL) in diethyl ether (will use "ether" from here)
(200 mL) at -78 C. After the addition, the cold bath was removed and the
slurry was allowed to warm to room temperature over 2 hours. The slurry
was filtered and the filtrate was pumped to dryness. The residue was
distilled (500 microns, 55 C) to give the product in quantitative yield. 'H
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NMR (6, toluene-d8): 2.66 (doublet of a quartets, 4H, JPH = 13 Hz, JHH = 7
Hz), 0.75 (triplet, 6H, J = 7 Hz).
Preparation of (ortho-F-C6H4)2P-NEt2
To solution of n-BuLi (17.00 mL of 1.6 M n-BuLi hexane solution,
27.18 mmol) in ether (100 mL) maintained at -85 C, was added dropwise
a solution of 1-bromo-2-fluorobenzene (4.76 g, 27.18 mmol) in ether (40
mL) over 2 hours. After addition, the reaction flask was stirred for 1 hour
at -78 C, resulting in a white slurry. Et2NPCI2 (2.36 g, 13.58 mmol) in
ether (20 mL) was then added very slowly while the reaction temperature
was maintained at -85 C. The reaction was allowed to warm to -10 C
overnight. Toluene (10 mL) was then added to the reaction flask and the
volatiles were removed in vacuo. The residue was extracted with toluene
and the soiution was pumped to dryness. The crude product was distilled
(300 microns, 100 C) yielding 3.78 g (95%) of product. 'H NMR (6, THF--
d8): 7.40-7.01 (4 equal intense multiplets, 8H), 3.11 (doublets of quartet,
4H, JPH = 13 Hz, JHH = 7 Hz), 0.97 (triplet, 6H, J = 7 Hz). 19F NMR (6,
THF-d8): -163.21 (doublet of multiplets, J = 48 Hz). GC-MS. M+ = 293.
Preparation of (ortho-F-C6H4)2PCI
Anhydrous HCI(g) was introduced to the head space of an ethereal
solution (100 mL) of (ortho-F-C6H4)P-NEt2 (3.73 g, 12.70 mmol) to a
pressure of 3 psi. A white precipitate formed immediately. The reaction
was stirred for an additional 0.5 hrs at which point the slurry was pumped
to dryness to remove volatiles. The residue was re-slurried in ether (100
mL) and filtered. The filtrate was pumped to dryness yielding (ortho-F-
C6H4)2PCI as a colorless oil in quantitative yield. 'H NMR (6, THF-d8):
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7.60 (m, 4H), 7.20 (m, 2H), 7.08 (m, 2H). 19F NMR (S, THF-d8): -106.94
(doublet of multiplets, J = 67 Hz).
Preparation of (ortho-F-C6H4)2PNH i-Pr
To a solution of (orfho-F-C6H4)PCI (1.00 g, 3.90 mmol) in ether (50
mL) and NEt3 (3 mL) was added an ethereal solution of i-PrNH2 (0.42 mL,
4.90 mmol) at -5 C. Immediate precipitate was observed. The slurry was
stirred for 3 hours and filtered. The filtrate was pumped to dryness to give
a colorless oil of (ortho-F-C6H4)PNH(i-Pr) in quantitative yield.
'H NMR (8, THF-d8): 7.42 (m, 2H), 7.30 (m, 2H), 7.11 (m, 2H), 6.96 (m,
2H), 3.30 (septet, 1 H, J= 7 Hz), 2.86 (br s, 1 H), 1.15 (d, 6H, J = 7 Hz).
19F
NMR (6, THF-d8): -109.85 (doublet of multiplets, J = 40 Hz). GC-MS, M+ =
279.
Preparation of (ortho-F-C6H4)2PN(i-Pr)P(ortho-F-C6H4);I
To a solution of (ortho-F-C6H4)2PNH(i-Pr) (3.90 mmol) [made from i-
PrNH2 and (ortho-F-C6H4)2PCI (1.00 g, 3.90 mmol)] in ether (100 mL)
maintained at -70 C was added dropwise a solution of n-BuLi (2.43 mL of
1.6 M n-BuLi hexane solution, 3.90 mmol)). The mixture was stirred at -70
C for 1 hour and allowed to warm to -10 C in a cold bath (2 hrs). The
solution was re-cooled to -70 C and (ortho-F-C6H4)2PC1 was slowly
added. The solution was stirred for 1 hour at -70 C and allowed to slowly
warm to room temperature forming a white precipitate. The slurry was
pumped to dryness and the residue was extracted with toluene and
filtered. The filtrate was pumped to dryness and recrystallized from
heptane at -70 C (2x) yielding 1.13 g (58%) of product. At room
temperature this material is an oil. 'H NMR (S, THF-d8): two isomers with
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equal intensity. 8.01 (m, 1 H), 7.75 (m, 1 H), 7.41(m, 1 H), 7.29 (m, 1 H),
7.16 (m, 1 H), 7.02 (m, 1 H), 6.92 (m, 2H), slightly overlapping septets with
equal intensity at 3.43 ppm and 3.36 ppm with total integration of 1 H, 0.92
(overlapping doublet, 6H); 19F NMR (8, THF-d8): -103.57 (doublet of
multiplets, J=58 Hz), -104.65 (doublet of multiplets, J= 49 Hz).
Oligomerization Reactions
Example 1
A 600-mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (11.72 g, 10 wt% Al) in 57.31 g of
toluene, followed by 86.7 g of toluene was transferred via a stainless steel
cannula to the reactor. The reactor was then pressurized with ethylene
(15 atmospheres (gauge)) and the temperature adjusted to 45 C. Bis(di-
(ortho-fluorophenyl)phosphino)-i-propylamine (33.4 mg, 0.067 mmol) in
8.69 g of toluene was added to chromium acetylacetonate (22.9 mg, 0.066
mmol) in 8.68 g of toluene in a hypovial. The mixture was sonicated at
ambient temperature for 1 minute and then transferred under ethylene to
the pressurized reactor. Immediately after, additional ethylene was added
to increase the reactor pressure to 20 atmospheres (gauge). The reaction
was terminated after 12 minutes by stopping the flow of ethylene to the
reactor and cooling the contents to 30 C, at which point excess ethylene
was slowly released from the reactor cooling the contents to 0 C. The
product mixture was transferred to a pre-weighed flask containing 1g of
ethanol. A sample of the liquid product was analyzed by GC. The solid
products were collected, weighed and dried at ambient temperature. The
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mass of the total product was obtained by summing the weight of liquid
and wet solid fractions (50.2 g) (Example 1, Table 1).
Example 2
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 75 C. The reactor was then
cooled to 30 C and a solution of MAO (11.69 g, 10 wt% Al) in 57.41 g
toluene, followed by 86.62 g of toluene was transferred via a stainless
steel cannula to the reactor. The reactor was then pressurized with
ethylene (15 atmospheres (gauge)) and the temperature adjusted to 70
C. Bis(di-(ortho-fluorophenyl)phosphino)-i-propylamine (33.5 mg, 0.067
mmol) in 8.69 g of toluene was added to chromium acetylacetonate (22.8
mg, 0.065 mmol) in 8.70 g of toluene in a hypovial. The mixture was
sonicated at ambient temperature for 1 minute and then transferred under
ethylene to the pressurized reactor. Immediately after, additional ethylene
was added to increase the reactor pressure to 20 atmospheres (gauge).
The reaction was terminated after 21 minutes by stopping the flow of
ethylene to the reactor and cooling the contents to 30 C, at which point
excess ethylene was slowly released from the reactor cooling the contents
to 0 C. The product mixture was transferred to a pre-weighed flask
containing 1 g of ethanol. A sample of the liquid product was analyzed by
GC. The solid products were collected, weighed and dried at ambient
temperature. The mass of the total product was obtained by summing the
weight of liquid and wet solid fractions (28.0 g) (Example 2, Table 1).
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Example 3
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (11.70 g, 10 wt% Al) in 57.32 g
toluene, followed by 86.7 g of toluene was transferred via a stainless steel
cannula to the reactor. The reactor was then pressurized with ethylene
(35 atmospheres (gauge)) and the temperature adjusted to 45 C. Bis(di-
(ortho-fluorophenyl)phosphino)-i-propylamine (33.5 mg, 0.067 mmol) in
8.70 g of toluene was added to chromium acetylacetonate (22.8 mg, 0.0611)
mmol) in 8.68 g of toluene in a hypovial. The mixture was sonicated at
ambient temperature for 1 minute and then transferred under ethylene to
the pressurized reactor. Immediately after, additional ethylene was added
to increase the reactor pressure to 40 atmospheres (gauge). The reaction
was terminated after 5 minutes by stopping the flow of ethylene to the
reactor and cooling the contents to 30 C, at which point excess ethylene
was slowly released from the reactor cooling the contents to 0 C. The
product mixture was transferred to a pre-weighed flask containing 1 g of
ethanol. A sample of the liquid product was analyzed by GC. The solid
products were collected, weighed and dried at ambient temperature. The
mass of the total product was obtained by summing the weight of liquid
and wet solid fractions (47.2 g) (Example 3, Table 1).
Example 4
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (5.90 g, 10 wt% Al) in 63.22 g
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toluene, followed by 86.62 g of toluene was transferred via a stainless
steel cannula to the reactor. The reactor was then pressurized with
ethylene (35 atmospheres (gauge)) and the temperature adjusted to 45
C. Bis(di-(ortho-fluorophenyl)phosphino)-i-propylamine (17.42 mg, 0.035
mmol) in 8.69 g of toluene was added to chromium acetylacetonate (11.78
mg, 0.034 mmol) in 8.69 g of toluene in a hypovial. The mixture was
sonicated at ambient temperature for 1 minute and then transferred under
ethylene to the pressurized reactor. Immediately after, additional ethylene
was added to increase the reactor pressure to 40 atmospheres (gauge).
The reaction was terminated after 10 minutes by stopping the flow of
ethylene to the reactor and cooling the contents to 30 C, at which point
excess ethylene was slowly released from the reactor cooling the contents
to 0 C. The product mixture was transferred to a pre-weighed flask
containing 1 g of ethanol. A sample of the liquid product was analyzed by
GC. The solid products were collected, weighed and dried at ambient
temperature. The mass of the total product was obtained by summing the
weight of liquid and wet solid fractions (64.3 g) (Example 4a, Table 1).
This experiment was repeated twice more to ensure reproducibility
(Examples 4b & 4c, Table 1).
Example 5
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (6.15 g, 10 wt% Al) in 62.87 g
toluene, followed by 86.7 g of toluene was transferred via a stainless steel
cannula to the reactor. The reactor was then pressurized with ethylene
34
M:\Scott\SCSpec\2007008Can.doc

CA 02583007 2007-03-29
(15 atmospheres (gauge)) and the temperature adjusted to 45 C. Bis(di-
(ortho-fluorophenyl)phosphino)-i-propylamine (17.42 mg, 0.035 mmol) in
8.69 g of toluene was added to chromium acetylacetonate (11.79 mg,
0.034 mmol) in 8.68 g of toluene in a hypovial. The mixture was sonicated
at ambient temperature for 1 minute and then transferred under ethylene
to the pressurized reactor. Immediately after, additional ethylene was
added to increase the reactor pressure to 20 atmospheres (gauge). The
reaction was terminated after 20 minutes by stopping the flow of ethylene
to the reactor and cooling the contents to 30 C, at which point excess
ethylene was slowly released from the reactor cooling the contents to 0 C.
The product mixture was transferred to a pre-weighed flask containing 1 g
of ethanol. A sample of the liquid product was analyzed by GC. The solid
products were collected, weighed and dried at ambient temperature. The
mass of the total product was obtained by summing the weight of liquid
and wet solid fractions (40.3 g) (Example 5a, Table 1). See Example 5b,
Table I for repeat run.
Example 6
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (6.05 g, 10 wt% Al) in 62.97 g
toluene, followed by 86.7 g of toluene was transferred via a stainless steel
cannula to the reactor. The reactor was then pressurized with ethylene (5
atmospheres (gauge)) and the temperature adjusted to 45 C. Bis(di-
(ortho-fluorophenyl)phosphino)-i-propylamine (17.53 mg, 0.035 mmol) in
8.73 g of toluene was added to chromium acetylacetonate (11.62 mg,
M:\Scott\SCSpec\2007008Ca n.doc

CA 02583007 2007-03-29
0.033 mmol) in 8.70 g of toluene in a hypovial. The mixture was sonicated
at ambient temperature for 1 minute and then transferred under ethylene
to the pressurized reactor. Immediately after, additional ethylene was
added to increase the reactor pressure to 10 atmospheres (gauge). The
reaction was terminated after 20 minutes by stopping the flow of ethylene
to the reactor and cooling the contents to 30 C, at which point excess
ethylene was slowly released from the reactor cooling the contents to 00C.
The product mixture was transferred to a pre-weighed flask containing 1 g
of ethanol. A sample of the liquid product was analyzed by GC. The solid
products were collected, weighed and dried at ambient temperature. The
mass of the total product was obtained by summing the weight of liquid
and wet solid fractions (6.5 g) (Example 6, Table 1).
Comparative Example
Example 7
A 600 mL reactor fitted with a gas-entrained stirrer (1700 rpm) was
purged 3 times with argon while heated at 50 C. The reactor was then
cooled to 30 C and a solution of MAO (6.09 g, 10 wt% Al) in 62.92 g
toluene, followed by 86.7 g of toluene was transferred via a stainless steel
cannula to the reactor. The reactor was then pressurized with ethylene
(35 atmospheres (gauge)) and the temperature adjusted to 45 C.
Bis(diphenyl)phosphino)-i-propylamine (15.29 mg, 0.036 mmol) in 10.69 g
of toluene was added to chromium acetylacetonate (11.74 mg, 0.034
mmol) in 8.71 g of toluene in a hypovial. The mixture was sonicated at
ambient temperature for 1 minute and then transferred under ethylene to
the pressurized reactor. Immediately after, additional ethylene was added
36
M:\Scott\SCSpec\2007008Can.doc

CA 02583007 2007-03-29
to increase the reactor pressure to 40 atmospheres (gauge). The reaction
was terminated after 16 minutes by stopping the flow of ethylene to the
reactor and cooling the contents to 30 C, at which point excess ethylene
was slowly released from the reactor cooling the contents to 0 C. The
product mixture was transferred to a pre-weighed flask containing 1 g of
ethanol. A sample of the liquid product was analyzed by GC. The solid
products were collected, weighed and dried at ambient temperature. The
mass of the total product was obtained by summing the weight of liquid
and wet solid fractions (63.7 g) (Example 7, Table 1).
37
M:\Scott\SCSpec\2007008Can.doc

CA 02583007 2007-03-29
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Dessin représentatif

Désolé, le dessin représentatif concernant le document de brevet no 2583007 est introuvable.

États administratifs

2024-08-01 : Dans le cadre de la transition vers les Brevets de nouvelle génération (BNG), la base de données sur les brevets canadiens (BDBC) contient désormais un Historique d'événement plus détaillé, qui reproduit le Journal des événements de notre nouvelle solution interne.

Veuillez noter que les événements débutant par « Inactive : » se réfèrent à des événements qui ne sont plus utilisés dans notre nouvelle solution interne.

Pour une meilleure compréhension de l'état de la demande ou brevet qui figure sur cette page, la rubrique Mise en garde , et les descriptions de Brevet , Historique d'événement , Taxes périodiques et Historique des paiements devraient être consultées.

Historique d'événement

Description Date
Exigences relatives à la révocation de la nomination d'un agent - jugée conforme 2021-02-25
Exigences relatives à la nomination d'un agent - jugée conforme 2021-02-25
Demande visant la révocation de la nomination d'un agent 2020-12-15
Demande visant la nomination d'un agent 2020-12-15
Représentant commun nommé 2019-10-30
Représentant commun nommé 2019-10-30
Accordé par délivrance 2015-03-31
Inactive : Page couverture publiée 2015-03-30
Préoctroi 2015-01-07
Inactive : Taxe finale reçue 2015-01-07
Un avis d'acceptation est envoyé 2014-11-27
Lettre envoyée 2014-11-27
Un avis d'acceptation est envoyé 2014-11-27
Inactive : Approuvée aux fins d'acceptation (AFA) 2014-11-07
Inactive : Q2 réussi 2014-11-07
Modification reçue - modification volontaire 2014-08-04
Inactive : Dem. de l'examinateur par.30(2) Règles 2014-02-10
Inactive : Rapport - Aucun CQ 2014-01-24
Modification reçue - modification volontaire 2013-09-27
Inactive : Dem. de l'examinateur par.30(2) Règles 2013-04-11
Lettre envoyée 2012-03-20
Toutes les exigences pour l'examen - jugée conforme 2012-03-12
Exigences pour une requête d'examen - jugée conforme 2012-03-12
Requête d'examen reçue 2012-03-12
Demande publiée (accessible au public) 2008-09-29
Inactive : Page couverture publiée 2008-09-28
Inactive : CIB en 1re position 2007-06-27
Inactive : CIB attribuée 2007-06-27
Inactive : Inventeur supprimé 2007-04-26
Lettre envoyée 2007-04-26
Inactive : Certificat de dépôt - Sans RE (Anglais) 2007-04-26
Demande reçue - nationale ordinaire 2007-04-26

Historique d'abandonnement

Il n'y a pas d'historique d'abandonnement

Taxes périodiques

Le dernier paiement a été reçu le 2014-12-12

Avis : Si le paiement en totalité n'a pas été reçu au plus tard à la date indiquée, une taxe supplémentaire peut être imposée, soit une des taxes suivantes :

  • taxe de rétablissement ;
  • taxe pour paiement en souffrance ; ou
  • taxe additionnelle pour le renversement d'une péremption réputée.

Les taxes sur les brevets sont ajustées au 1er janvier de chaque année. Les montants ci-dessus sont les montants actuels s'ils sont reçus au plus tard le 31 décembre de l'année en cours.
Veuillez vous référer à la page web des taxes sur les brevets de l'OPIC pour voir tous les montants actuels des taxes.

Titulaires au dossier

Les titulaires actuels et antérieures au dossier sont affichés en ordre alphabétique.

Titulaires actuels au dossier
NOVA CHEMICALS CORPORATION
Titulaires antérieures au dossier
CHARLES ASHTON GARRET CARTER
LEE DOUGLAS HENDERSON
LIANGYOU FAN
XIAOLIANG GAO
Les propriétaires antérieurs qui ne figurent pas dans la liste des « Propriétaires au dossier » apparaîtront dans d'autres documents au dossier.
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Description du
Document 
Date
(aaaa-mm-jj) 
Nombre de pages   Taille de l'image (Ko) 
Revendications 2013-09-26 3 68
Description 2007-03-28 37 1 390
Abrégé 2007-03-28 1 15
Revendications 2007-03-28 4 81
Revendications 2014-08-03 3 64
Abrégé 2014-08-03 1 14
Courtoisie - Certificat d'enregistrement (document(s) connexe(s)) 2007-04-25 1 105
Certificat de dépôt (anglais) 2007-04-25 1 158
Rappel de taxe de maintien due 2008-12-01 1 112
Rappel - requête d'examen 2011-11-29 1 117
Accusé de réception de la requête d'examen 2012-03-19 1 177
Avis du commissaire - Demande jugée acceptable 2014-11-26 1 161
Correspondance 2015-01-06 1 40